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1,3-Diynes are frequently found as an important structural motif in natural products, pharmaceuticals and bioactive compounds, electronic and optical materials and supramolecular molecules. Copper and palladium complexes are widely used to prepare 1,3-diynes by homocoupling of terminal alkynes; albeit the potential of nickel complexes towards the same is essentially unexplored. Although a detailed study on the reported nickel-acetylene chemistry has not been carried out, a generalized mechanism featuring a nickel(II)/nickel(0) catalytic cycle has been proposed. In the present work, a detailed mechanistic aspect of the nickel-mediated homocoupling reaction of terminal alkynes is investigated through the isolation and/or characterization of key intermediates from both the stoichiometric and the catalytic reactions. A nickel(II) complex [Ni(L-N4Me2)(MeCN)2](ClO4)2 (1) containing a tetradentate N,N′-dimethyl-2,11-diaza[3.3](2,6)pyridinophane (L-N4Me2) as ligand was used as catalyst for homocoupling of terminal alkynes by employing oxygen as oxidant at room temperature. A series of dinuclear nickel(I) complexes bridged by a 1,3-diyne ligand have been isolated from stoichiometric reaction between [Ni(L-N4Me2)(MeCN)2](ClO4)2 (1) and lithium acetylides. The dinuclear nickel(I)-diyne complexes [{Ni(L-N4Me2)}2(RC4R)](ClO4)2 (2) were well characterized by X-ray crystal structures, various spectroscopic methods, SQUID and DFT calculation. The complexes not only represent as a key intermediate in aforesaid catalytic reaction, but also describe the first structurally characterized dinuclear nickel(I)-diyne complexes. In addition, radical trapping and low temperature UV-Vis-NIR experiments in the formation of the dinuclear nickel(I)-diyne confirm that the reactions occurring during the reduction of nickel(II) to nickel(I) and C-C bond formation of 1,3-diyne follow non-radical concerted mechanism. Furthermore, spectroscopic investigation on the reactivity of the dinuclear nickel(I)-diyne complex towards molecular oxygen confirmed the formation of a mononuclear nickel(I)-diyne species [Ni(L-N4Me2)(RC4R)]+ (4) and a mononuclear nickel(III)-peroxo species [Ni(L-N4Me2)(O2)]+ (5) which were converted to free 1,3-diyne and an unstable dinuclear nickel(II) species [{Ni(L-N4Me2)}2(O2)]2+ (6). A mononuclear nickel(I)-alkyne complex [Ni(L-N4Me2)(PhC2Ph)](ClO4).MeOH (3) and the mononuclear nickel(III)-peroxo species [Ni(L-N4Me2)(O2)]+ (5) were isolated/generated and characterized to confirm the formulation of aforementioned mononuclear nickel(I)-diyne and mononuclear nickel(III)-peroxo species. Spectroscopic experiments on the catalytic reaction mixture also confirm the presence of aforesaid intermediates. Results of both stoichiometric and catalytic reactions suggested an intriguing mechanism involving nickel(II)/nickel(I)/nickel(III) oxidation states in contrast to the reported nickel(II)/nickel(0) catalytic cycle. These findings are expected to open a new paradigm towards nickel-catalyzed organic transformations.